JPS6231981B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention uses molybdenum alone or molybdenum.
This invention relates to a method for producing a coal liquefaction catalyst from alloy steel containing 0.3% by weight or more. Conventionally, Co-Mo based catalysts, Co-Mo based catalysts,
Examples include catalysts made of metal halides and red mud-sulfur, but these catalysts have a significant drop in catalytic activity, cannot withstand long-term use, are difficult to regenerate, and are relatively expensive. The present invention was made in view of the above circumstances, and
The object of the present invention is to provide a catalyst that solves the problem of catalyst activity deterioration, is easy to regenerate, and can be suitably employed mainly for coal liquefaction. That is, the production method of the present invention involves adding alkali and water to molybdenum salts or oxides or alloy steel containing 0.3% by weight or more of molybdenum, and then treating the mixture at a temperature of 220°C to 450°C in a carbon monoxide atmosphere. The product is washed with water, dried, and then reduced at a temperature of 400°C to 450°C by adding an appropriate amount of tetralin and/or a phenol compound under a hydrogen atmosphere. The alloy steel that can be used in the present invention may be one containing 0.3% by weight or more of molybdenum, such as SCM, SKH, SUS, etc., but from the viewpoint of the mechanical strength and economic efficiency of the obtained catalyst In other words, iron-chromium-molybdenum type materials are preferred. The molybdenum content is preferably as high as 0.3% by weight or more. As the salts, any of ammonium salts, nitrates, chlorides, carbonates, and organic acid salts can be used, but ammonium salts are preferred. Further, as the oxide, trioxide can be suitably used. Also, as an alkali, the general formula
Any material shown by MOH may be used. Furthermore, this M
usually indicates an alkali metal or ammonium group,
Also includes calcium, barium, sodium carbonate, ammonium carbonate, and sodium phosphate. As the phenol compound, either monohydric phenol or polyhydric phenol can be used. For reduction in a hydrogen atmosphere, the initial hydrogen pressure is preferably 50 kg/cm ² or more. At 50Kg/cm ² the reaction rate is extremely low. Note that a carrier may be introduced, but in that case, before adding the alkal and water in the above manufacturing process,
It may be mixed with the above salts or oxides. The carrier may be any carrier as long as it has a cocatalytic effect.
Diatomaceous earth, pumice, activated carbon, silica gel, alimina, etc. can be used. Further, at any stage of the above manufacturing process, an appropriate binder may be added as necessary to shape the obtained catalyst into an appropriate shape. It goes without saying that the catalyst obtained by the production method of the present invention as described above can be applied not only to the liquefaction of coal but also to the lightening of heavy petroleum oil. Next, examples of the present invention will be shown, but the following examples are not intended to limit the present invention. Example 1 Add 10 g of sodium hydroxide and 5 ml of water to 10 g of ammonium molybdate, heat at about 50°C until the ammonium odor disappears, and then heat at 420°C in a carbon monoxide atmosphere (100 Kg/cm ² ). Heat treatment was performed for 1 hour. The reaction product thus obtained was thoroughly washed with warm water and then dried at 100±5°C until absolutely dry. Next, 2 g of catechol and 50 g of tetralin were added to 8 g of this dried reaction product.
ml, under hydrogen atmosphere (100Kg/cm ² ), temperature 420
The reaction product obtained by reduction at °C was filtered, and the filtered product was dried at 130 °C overnight. A catalyst was thus obtained (yield: 7.5 g). Add 1 g of the catalyst thus obtained to 10 g of coal, and further add 15 g of diphenyl ether, under hydrogen atmosphere (initial pressure 30 Kg/cm ² ), at a temperature of 400°C to
Hydrogen decomposition was carried out at 430°C, and n-hexane was extracted by standing at room temperature. The amount of n-hexane extracted from the n-hexane extraction residue was determined, and this was used as an index of the liquefaction rate. The results are shown in Table 1. For comparison, the amount of n-hexane extracted without using a catalyst is also shown.

【table】

[Table] Example 2 A catalyst was obtained in the same manner as in Example 1, except that SCM-3 (molybdenum content: 0.3% by weight) was used as a molybdenum-containing alloy steel instead of ammonium molybdate. The catalyst obtained in this way was prepared using tetralin instead of diphenyl ether, and the initial pressure of hydrogen was 60.
Pacific coal was liquefied in the same manner as in Example 1 except that the amount was changed to Kg/cm ² . The results are shown in Table 2.

[Table] Example 3 A catalyst was obtained in the same manner as in Example 1, except that SUS316 (molybdenum content: 3 to 5% by weight) was used as a molybdenum-containing alloy steel instead of ammonium molybdate. The catalyst obtained in this way was prepared using tetralin instead of diphenyl ether, and the initial pressure of hydrogen was 60.
Pacific coal was liquefied in the same manner as in Example 1 except that the amount was changed to Kg/cm ² . The results are shown in Table 3.

[Table] Example 4 SKH9 (molybdenum content 6
A catalyst was obtained in the same manner as in Example 1 except that % by weight) was used. The catalyst obtained in this way was prepared using tetralin instead of diphenyl ether, and the initial pressure of hydrogen was 60.
Pacific coal was liquefied in the same manner as in Example 1 except that the amount was changed to Kg/cm ² . The results are shown in Table 4.

[Table] It is understood that when coal is liquefied using the catalyst obtained by the production method of the present invention as described above, the liquefaction rate is extremely high. Moreover, it has the advantage that the reaction pressure can also be lowered. Furthermore, even if Pacific coal is directly liquefied using the catalyst obtained in Example 1 without using a medium oil such as diphenyl ether, the liquefaction rate is higher than when a conventional catalyst is used, and the reaction pressure is also lower. Can be made lower. Note that even if the catalysts obtained in Examples 2 to 4 deteriorate, they can be regenerated extremely easily. Moreover, when these catalysts are washed with acid, their catalytic activity is deactivated, and is restored by performing the treatment again.

Claims (1)

[Claims] 1 Add alkali and water to molybdenum salts or oxides or alloy steel containing 0.3% by weight or more of molybdenum, and then treat the product at a temperature of 220°C to 450°C in a carbon monoxide atmosphere and wash the resulting product with water. A method for producing a catalyst for coal liquefaction, which comprises drying, adding an appropriate amount of tetralin and/or a phenol compound in a hydrogen atmosphere, and reducing at a temperature of 400°C to 450°C.